Chiral diphosphorus compounds and their transition metal complexes

ABSTRACT

The present invention relates to chiral diphosphorus compounds and their transition metal complexes, to a process for preparing chiral diphosphorus compounds and their transition metal complexes and also to their use in asymmetric syntheses.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to chiral diphosphorus compounds and theirtransition metal complexes, to a process for preparing chiraldiphosphorus compounds and their transition metal complexes and also totheir use in asymmetric syntheses.

2. Brief Description of the Prior Art

Enantiomerically enriched chiral compounds are valuable startingsubstances for preparing agrochemicals and pharmaceuticals. Asymmetriccatalysis for the synthesis of such enantiomerically enriched chiralcompounds has gained great industrial significance.

The multitude of publications in the field of asymmetric synthesis showsclearly that transition metal complexes of diphosphorus compounds areparticularly suitable as catalysts in asymmetric reactions. Inparticular, transition metal complexes of diphosphorus compounds havefound use in industrial processes as catalysts in asymmetrichydrogenations of C═O, C═N and C═C bonds, hydrocyanations andhydroformylations.

For instance, U.S. Pat. No. 5,175,335; Rajan Babu, J. Am. Chem. Soc.,1996, 118, 6325-6326 and Rajan Babu, J. Org. Chem., 1997, 62, 6012-6028disclose the use of enantiomerically enriched 1,6-substituted3,4-(bisphosphinito)tetrahydrofurans and their transition metalcomplexes for asymmetric hydrocyanations and hydrogenations.

The use of the enantiomerically enriched 3,4-(bisphosphino)tetrahydrofurans and their transition metal complexes in asymmetrichydrogenations is also disclosed by EP-A 885 897 and A. Terfort,Synthesis, 1992, 10, 951-953. Enantiomerically enriched3,4-(bisphosphito)tetrahydrofurans are described, for example, in W. R.Jackson, Aust. J. Chem., 1982, 35, 2069-2075 and,3,4-(phosphinophosphito)tetrahydrofurans in A. Kless, Tetrahedron:Asymmetry, 1996, 7, 33-36.

The disadvantage of all of the enantiomerically enriched3,4-(diphosphorus)-tetrahydrofurans mentioned is that steric andelectronic variation of the central tetrahydrofuran framework, which isnecessary for precise optimization and adaptation of the ligand andtherefore of the catalyst for a given substrate, is only possible to avery limited extent and by numerous, complex synthetic steps. Thesedisadvantages make industrial utilisation of such ligands and thecatalysts preparable therefrom uneconomic.

There is therefore a need to develop a ligand system whose steric andelectronic properties can be easily varied, and whose transition metalcomplexes as catalysts in asymmetric synthesis, in particular asymmetrichydrogenations, enable not only high enantioselectivity but also highconversion rates.

SUMMARY OF THE INVENTION

Diphosphorus compounds of the formula (I) have now been found

where

-   *1, *2, *3 and *4 are each independently a stereogenic carbon atom    which is in the R- or S-configuration,-   X¹ and X² are each independently absent or are oxygen and-   R¹ and R² may each independently be: hydrogen, C₁-C₂₀-alkyl,    C₁-C₂₀-fluoroalkyl, C₂-C₂₀-alkenyl, C₄-C₂₄-aryl, C₅-C₂₅-arylalkyl,    C₆-C₂₆-arylalkenyl or NR⁷R⁸, OR⁸, —(C₁-C₈-alkyl)-OR⁸,    —(C₁-C₈-alkyl)-NR⁷R⁸ or —O₂CR⁸-   where R⁷ and R⁸ are each independently C₁-C₈-alkyl, C₅-C₁₅-arylalkyl    or C₄-C₁₄-aryl, or R⁷ and R⁸ together are a cyclic amino radical    having a total of 4 to 20 carbon atoms,-   or R¹ and R² are each independently radicals of the formula (II)    —R⁹—SiR¹⁰R¹¹R¹²  (II)    where-   R⁹ is absent, or is oxygen or methylene and-   R¹⁰, R¹¹ and R¹² are each independently C₁-C₁₂-alkyl,    C₅-C₁₅-arylalkyl or C₄-C₁₄-aryl and-   R³, R⁴, R⁵ and R⁶ are each independently R¹³, OR¹⁴ or NR¹⁵R¹⁶ where    R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently C₁-C₁₂-alkyl,    C₅-C₁₅-arylalkyl or C₄-C₁₄-aryl, or NR¹⁵R¹⁶ together is a cyclic    amino radical having 4 to 20 carbon atoms, or R³ and R⁴ and/or R⁵    and R⁶ in each case together are —O—R¹⁷—O— where R¹⁷ is a radical    selected from the group of C₂-C₄-alkylene, 1,2-phenylene,    1,3-phenylene, 1,2-cyclohexylene, 1,1′-ferrocenylene,    1,2-ferrocenylene, 2,2′-(1,1′-binaphthylene),    2,2′-(1,1′)-biphenylene and 1,1′-(diphenyl-2,2′-methylene)-diyl, and    the radicals mentioned may optionally be mono- or polysubstituted by    radicals selected from the group of fluorine, chlorine, C₁-C₈-alkoxy    and C₁-C₈-alkyl.

For the purposes of the invention, all radical definitions, parametersand illustrations mentioned hereinabove and hereinbelow, generally or inareas of preference, i.e. the particular areas and areas of preference,may be combined as desired.

DETAILED DESCRIPTION OF THE INVENTION

Alkyl, alkylene, alkoxy and alkenyl are in each case independently astraight-chain, cyclic, branched or unbranched alkyl, alkylene, alkoxyand alkenyl radical respectively. The same applies to the nonaromaticmoiety of an arylalkyl radical.

C₁-C₄-Alkyl is, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl and tert-butyl, C₁-C₈-alkyl is additionally, forexample, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl and n-octyl, C₁-C₁₂-alkyl is further additionally, for example,adamantyl, the isomeric menthyls, n-nonyl, n-decyl and n-dodecyl, andC₁-C₂₀-alkyl is still further additionally, for example, n-hexadecyl andn-octadecyl.

C₁-C₈-Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec-butoxy and tert-butoxy, n-pentoxy, 1-methylbutoxy,2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexoxy,cyclopentoxy, n-hexoxy and n-octoxy, and C₁-C₁₂-alkoxy is furtheradditionally, for example, adamantoxy, the isomeric menthoxy radicals,n-decoxy and n-dodecoxy.

C₂-C₂₀-Alkenyl is, for example, vinyl, 1-propenyl, isopropenyl,1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl,2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 1-heptenyl, 1-octenylor 2-octenyl.

Fluoroalkyl is in each case independently a straight-chain, cyclic,branched or unbranched alkyl radical which is singly, multiply or fullysubstituted by fluorine atoms.

C₁-C₂₀-fluoroalkyl is, for example, trifluoromethyl,2,2,2-trifluoroethyl, pentafluoroethyl, nonafluorobutyl, perfluorooctyl,perfluorododecyl and perfluorohexadecyl.

Aryl is in each case independently a heteroaromatic radical having 5 to18 framework carbon atoms of which no, one, two or three frameworkcarbon atoms per cycle, but at least one framework carbon atom in theentire molecule, may be substituted by heteroatoms selected from thegroup of nitrogen, sulphur or oxygen, but is preferably a carbocyclicaromatic radical having 6 to 18 framework carbon atoms.

Examples of carbocyclic aromatic radicals having 6 to 18 frameworkcarbon atoms are phenyl, naphtyl, phenanthrenyl, anthracenyl orfluorenyl, and heteroaromatic radicals having 5 to 18 framework carbonatoms on which no, one, two or three framework carbon atoms per cycle,but at least one framework carbon atom in the entire molecule, may besubstituted by heteroatoms selected from the group of nitrogen, sulphuror oxygen are, for example, pyridinyl, oxazolyl, benzofuranyl,dibenzofuranyl or quinolinyl.

The carbocyclic aromatic radical or heteroaromatic radical may also besubstituted by up to five identical or different substituents per cyclewhich are selected from the group of chlorine, fluorine, C₁-C₁₂-alkyl,C₁-C₁₂-fluoroalkyl, C₁-C₁₂-alkoxy, di(C₁-C₈-alkyl)amino,COO(C₁-C₈-alkyl), CON(C₁-C₈-alkyl)₂, COO(C₁-C₈-arylalkyl),COO(C₄-C₁₄-aryl), CO(C₁-C₈-alkyl), C₅-C₁₅-arylalkyl ortri(C₁-C₆-alkyl)siloxyl.

The same applies to aryloxy radicals.

Arylalkyl is in each case independently a straight-chain, cyclic,branched or unbranched alkyl radical which may be singly, multiply orfully substituted by aryl radicals as defined above.

C₅-C₂₅-Arylalkyl is, for example, benzyl, diphenylbenzyl,triphenylbenzyl (trityl), 1-phenylethyl, 1-phenylpropyl, 2-phenylpropyl,1-phenyl-1-methylethyl, 1-, 2-, 3- or 4-phenylbutyl,1-phenyl-1-methylpropyl, 1-phenyl-2-methylpropyl,phenyl-1,1-dimethylethyl, 1-,2-,3-,4- or 5-phenylpentyl,phenyl-1-methylbutyl, phenyl-2-methylbutyl, phenyl-3-methylbutyl,phenyl-2,2-dimethylpropyl, phenyl-1-ethylpropyl, 1-naphthylmethyl,1-naphthylethyl, naphthyl-1-methylethyl, naphthylbutyl,naphthyl-1-methylpropyl, naphthyl-2-methylpropyl,naphthyl-1,1-dimethylethyl, naphthylpentyl, naphthyl-1-methylbutyl,naphthyl-2-methylbutyl, naphthyl-3-methylbutyl,naphthyl-2,2-dimethylpropyl or naphthyl-1-ethylpropyl, and also theirisomeric or stereoisomeric forms.

Arylalkenyl is in each case independently a straight-chain, cyclic,branched or unbranched alkenyl radical which may be singly, multiply orfully substituted by aryl radicals as defined above.

C₆-C₂₆-Arylalkenyl is, for example, 1-phenylvinyl or 2-phenylvinyl.

The preferred substitution patterns or compounds of the formula (I) aredefined hereinbelow:

^(*1),^(*2),^(*3),^(*4) together define the following stereoisomers ofthe central substituted furan ring:

-   (1R,2R,3R,4R), (1R,2R,3R,4S), (1R,2R,3S,4S), (1R,2S,3S,4S),    (1R,2S,3R,4S), (1R,2S,3S,4R), (1R,2R,3S,4R), (1S,2S,3R,4S),    (1S,2S,3S,4S), (1S,2S,3S,4R), (1S,2S,3R,4R), (1S,2R,3R,4R),    (1S,2R,3S,4R), (1S,2R,3R,4S), (1S,2S,3R,4S), (1R,2R,3S,4R),    preferably (1R,2R,3R,4R), (1R,2R,3R,4S), (1R,2S,3S,4S),    (1R,2S,3S,4R), (1R,2R,3S,4R), (1S,2S,3R,4S), (1S,2S,3S,4S),    (1S,2S,3S,4R), (1S,2R,3R,4R), (1S,2R,3R,4S), (1S,2S,3R,4S),    (1R,2R,3S,4R).-   R¹ and R² are preferably each independently hydrogen, C₁-C₄-alkyl,    C₄-C₁₄-aryl, O—R⁸, O₂C—R⁸, where R⁸ is preferably C₁-C₁₂-alkyl,    C₅-C₂₅-arylalkyl or C₄-C₁₄-aryl, or OSiR¹⁰R¹¹R¹², where R¹⁰, R¹¹,    and R¹² are preferably each independently C₁-C₁₂-alkyl or    C₄-C₁₄-aryl.-   R¹ and R² are more preferably each independently hydrogen,    tert-butoxy, trityloxy, tert-butyldimethylsilyloxy,    tert-butyldiphenylsilyloxy, trimethylsilyloxy, triethylsilyloxy,    triisopropylsilyloxy, neopentoxy or 1-adamantoxy.

For the purposes of the invention, preference is in each case given tothose compounds of the formula (I) in which R¹ and R² are identical.

R³, R⁴, R⁵ and R⁶ are preferably each independently R¹³, OR¹⁴ or NR¹⁵R¹⁶where R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently C₁-C₁₂-alkyl orC₄-C₁₄-aryl, or NR¹⁵R¹⁶ together is a cyclic amino radical having 4 to12 carbon atoms, for example pyrrolidinyl or piperidinyl, or R³ and R⁴and/or R⁵ and R⁶ together are each —O—R¹⁷—O— where R¹⁷ is ethylene,1,2-phenylene, 1,3-phenylene, 1,2-cyclohexylene, 1,1′-ferrocenylene,1,2-ferrocenylene, di- or tetra-C₁-C₈-alkyl-substituted1,1′-(diphenyl-2,2′-methylene)-diyl, 2,2′-(1,1′-binaphthylene) or2,2′-(1,1′)-biphenylene, and 2,2′-(1,1′-binaphthylene) or2,2′-(1,1′)-biphenylene is substituted at least in the 6,6′-position byradicals selected from the group of C₁-C₈-alkoxy and C₁-C₈-alkyl, andmay also be substituted in the 5,5′-, 4,4′-, 3,3′- or 2,2′-position byradicals selected from the group of fluorine, chlorine, C₁-C₈-alkoxy andC₁-C₈-alkyl.

R³, R⁴, R⁵ and R⁶ are more preferably each independently R¹³, OR¹⁴ orNR¹⁵R¹⁶, where R¹³ and R¹⁴ are each independently methyl, ethyl,n-propyl, isopropyl, tert-butyl, cyclohexyl, phenyl,2-(C₁-C₈)-alkylphenyl such as o-tolyl, 3-(C₁-C₈)-alkylphenyl such asm-tolyl, 4-(C₁-C₈)-alkylphenyl such as p-tolyl,2,6-di-(C₁-C₈)-alkylphenyl such as 2,6-dimethylphenyl,2,4-di-(C₁-C₈)-alkylphenyl such as 2,4-dimethylphenyl,3,5-di-(C₁-C₈)-alkylphenyl such as 3,5-dimethylphenyl,3,4,5-tri-(C₁-C₈)-alkylphenyl such as mesityl and isityl,2-(C₁-C₈)-alkoxyphenyl such as o-anisyl and o-phenetyl,3-(C₁-C₈)-alkoxyphenyl such as m-anisyl and m-phenetyl,4-(C₁-C₈)-alkoxyphenyl such as p-anisyl and p-phenetyl,2,4-di-(C₁-C₈)-alkoxyphenyl such as 2,4-dimethoxyphenyl,2,6-di-(C₁-C₈)-alkoxyphenyl such as 2,6-dimethoxyphenyl,3,5-di-(C₁-C₈)-alkoxyphenyl such as 3,5-dimethoxyphenyl,3,4,5-tri-(C₁-C₈)-alkoxyphenyl such as 3,4,5-trimethoxyphenyl,3,5-dialkyl-4-(C₁-C₈)-alkoxyphenyl such as 3,5-dimethyl-4-anisyl,3,5-(C₁-C₈)-dialkyl-4-di-(C₁-C₈)-alkylaminophenyl,3,5-dimethyl-4-dimethylamino-phenyl, 4-di-(C₁-C₈)-alkylaminophenyl suchas 4-diethylaminophenyl and 4-dimethylaminophenyl,3,5-bis-[(C₁-C₄)-fluoroalkyl]phenyl such as3,5-bis-trifluoromethylphenyl, 2,4-bis-[(C₁-C₄)-fluoroalkyl]phenyl suchas 2,4-bis-trifluoromethylphenyl, 4-[(C₁-C₄)-fluoroalkyl]phenyl such as4-trifluoromethylphenyl and mono-, di-, tri-, tetra- or penta-fluorine-and/or -chlorine-substituted phenyl, fluorenyl or naphthyl, such as4-fluorophenyl and 4-chlorophenyl, or NR¹⁵R¹⁶ as a whole isdimethylamino, diethylamino, pyrrolidino or diisopropylamino. R³ and R⁴and/or R⁵ and R⁶, each in pairs, are also more preferably O—R¹⁷—O whereR¹⁷ is 1,1′-bis-(4,6-di-(C₁-C₈-alkyl)-phenyl)-2,2′-methylene)-diyl, inparticular 1,1′-bis-(4-methyl-6-tert-butylphenyl-2,2′-methylene)-diyland1,1′-bis-(4-methyl-6-(1-methylcyclohexyl)-phenyl-2,2′-methylene)-diyl,or where R¹⁷ is (R)-1,1′-biphenyl-2,2′-diyl,(S)-1,1′-biphenyl-2,2′-diyl, (R)-1,1′-binaphthyl-2,2′-diyl,(S)-1,1′-binaphthyl-2,2′-diyl,1,1′-[bis-(4-methyl-6-tert-butylphenyl)-2,2′-methylene)]-diyl or1,1′-[bis-(4-methyl-6-(1-methylcyclohexyl)-2,2-methylene)]-diyl.

For the purposes of the invention, preference is given in each case tothose compounds of the formula (I) in which R³ and R⁴ and/or R⁵ and R⁶in pairs are identical.

Particularly preferred compounds of the formula (I) are those of theformulae (Ia) to (Ii)

where ^(*1), ^(*2), ^(*3), ^(*4), R¹, R², R¹³, R¹⁵ and R¹⁶ each have thedefinition and areas of preference specified under formula (I).

Compounds of the formula (I) include:2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-L-iditol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-L-iditol,2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-L-iditol,2,3-bis-O-(di(4-methoxyphenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(di((4-Trifluoromethyl)phenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol,2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol,2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(4,8-ditert-butyl-2,10-dimethyl-12H-dibenzo[δ,γ][1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitoland2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(2,10-dimethyl-4,8-bis(1-methylcyclohexyl)-12H-dibenzo[δ,γ]-[1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol.

For the purposes of the invention, the term stereoisomerically enrichedincludes in particular stereoisomerically pure compounds or elsemixtures of stereoisomeric compounds in which one stereoisomer ispresent in a larger relative proportion than the other stereoisomer orstereoisomers, preferably in a relative proportion of 50 to 100 mol %,more preferably 90 to 100 mol % and most preferably 98 to 100 mol %.

The compounds of the formula (I) and (Ia) to (Ii) can be preparedstarting from the known 2,5-anhydrocyclopentoses of the formula (III).

2,5-anhydrocyclopentoses of the formula (III) are, for example:2,5-anhydro-D-mannitol, 2,5-anhydro-L-mannitol, 2,5-anhydro-L-iditol,2,5-anhydro-D-iditol, 2,5-anhydro-L-glucitol, 2,5-anhydro-D-glucitol,2,5-anhydro-altritol, 2,5-anhydro-D-altritol, 2,5-anhydro-galactitol,2,5-anhydro-allitol.

Preferred compounds of the general formula (III) are:2,5-anhydro-D-mannitol and 2,5-anhydro-L-iditol. For the purposes of thepresent invention, preference is given in particular to those compoundsof the formula (I) which are obtainable starting from2,5-anhydro-D-mannitol and 2,5-anhydro-L-iditol by the methods describedhereinbelow.

The compounds of the formula (III) can be converted by reacting withcompounds of the formula (IV)R¹⁸-Hal  (IV)where

-   R¹⁸ is R⁸, R⁸CO or OSiR¹⁰R¹¹R¹² and where R⁸, R¹⁰, R¹¹ and R¹² each    have the definition and areas of preference specified under (I) or    R¹⁸ is R¹⁹⁻SO₂— where R¹⁹ is C₁-C₁₂-alkyl, C₁-C₁₂-fluoroalkyl,    C₅-C₂₅-arylalkyl or C₄-C₂₄-aryl and-   Hal is chlorine, bromine or iodine to compounds of the formula (V)    where R¹⁸ is in each case independently as defined under formula    (IV).

Compounds of the formula (V) where R¹⁸ is R¹⁹SO₂— can also be convertedby reacting with amines of the formula (VI)HNR⁷R⁸  (VI)where R⁷ and R⁸ each independently have the definitions and areas ofpreference specified under formula (I) to compounds of the formula (VII)

where R⁷ and R⁸ are each independently as defined under formula (IV).

Compounds of the formula (V) in which R¹⁸ is R¹⁹SO₂— can also beconverted by reacting with complex hydrides of the formula (VIII)Met¹(AlR²⁰ _(n)R²¹ _((4-n)))  (VIII)where Met¹ is lithium, sodium or potassium, preferably lithium,

-   R²⁰ is hydrogen-   n is 1, 2, 3 or 4, preferably 4 and-   R²⁰ is C₁-C₄-alkyl,    or by reacting organolithium compounds of the formula (IX)    R²⁰—Li  (IX)    where R²⁰ is C₁-C₂₀-alkyl, C₁-C₂₀-fluoroalkyl, C₂-C₂₀-alkenyl,    C₄-C₂₄-aryl, C₅-C₂₅-arylalkyl, C₆-C₂₆-arylalkenyl,    —(C₁-C₈-alkyl)-OR⁸, —(C₁-C₈-alkyl)-NR⁷R⁸ or protected (for example    as a cyclic acetal)-(C₁-C₈-alkyl)-CO—R⁸ to compounds of the formula    (X)    where R²⁰ is as defined under formulae (VIII) and (IX).

As a consequence of the acidity of the free 2- and 3-hydroxyl groups, itis advantageous to use an excess of the organolithium compounds or ofthe complex hydrides or to protect the 3,4-diol unit in a manner knownper se by conversion, for example, to a cyclic acetal, and subsequentlydeprotecting it again.

The compounds of the formulae (V), (VII) and (X) together areencompassed by the compounds of the formula (XI), which can be used asintermediates for preparing the compounds of the formula (I) accordingto the invention.

In formula (XI)

R¹ and R² each have the same definition and areas of preference asdescribed under formula (I).

The compounds of the formula (XI) can be used in a manner known inprinciple (see also Rajan Babu, J. Org. Chem., 1997, 62, 6012-6028), byreacting with compounds of the formula (XIIa)R³R⁴P—Y  (XIIa)where R³ and R⁴ each have the same definition and areas or preference asspecified under formula (I) and

-   Y is chlorine, bromine, iodine, dimethylamino or diethylamino,    preferably chlorine,    to obtain the compounds of the formula (XIII)    where R¹, R², R³ and R⁴ each have the same definition and areas of    preference as described under formula (I).

The compounds of the formula (XIII) can also be reacted with compoundsof the formula (XIIb)R⁵R⁶P—Y  (XIIb)where R⁵ and R⁶ each have the same definitions and areas of preferenceas specified under formula (I) and Y has the same definition and areasof preference as specified under formula (XIIa) to give compounds of theformula (XIV)

where R¹, R², R³, R⁴, R⁵ and R⁶ each have the same definitions and areasof preference as specified under formula (I).

When compound (XIIa) and (XIIb) are identical, the reaction can also becarried out in one step. Advantageously, the conversions of (XI) to(XIV), (XI) to (XIII) or (XIII) to (XIV) are carried out in the presenceof a base, for example amines or aromatic nitrogen bases such astriethylamine, pyridine or 4-dimethylaminopyridine. Alternatively, theconversion can also be effected after at least partial deprotonation ofthe alcohol functions.

Examples of suitable solvents for the conversions are chlorinatedalkanes such as methyl chloride, alkylic hydrocarbons, e.g. hexane,cyclohexane, aromatic hydrocarbons, e.g. toluene, pyridines, benzene,ketones, e.g. acetone, or carboxylic esters, e.g. ethyl acetate, ordialkyl ethers, e.g. THF or MTBE. The solvent used is preferablymethylene chloride.

In the manner described, the compounds of the formulae (Ia), (Id), (If),(Ig) and (Ii) in particular with the above-specified definition andareas of preference are obtainable.

The compounds of the formulae (XIII) and (XIV) are likewise encompassedby the invention. The same definitions and areas of preference apply asspecified under formula (I).

Compounds of the formula (XV)

where R¹, R², R⁵, R⁶ and R¹³ each have the definitions and areas ofpreference specified under formula (I) can also be prepared by a processaccording to the invention by converting compounds of the formula (XVI)

where R¹ and R² have the definition and areas of preference specifiedunder formula (I), in the presence of compounds of the formula (XVII)(R¹³)₂PMet²  (XVII)whereMet² is lithium, sodium or potassium and

-   R¹³ has the definition and areas of preference specified under    formula (I)    to compounds of the formula (XVIII)    where R¹, R², Met² and R¹³ are each as defined above,    and reacting the compounds of the formula (XVIII) with compounds of    the formula (XIIb) as defined there to give compounds of the formula    (XV).

Alternatively, the compounds of the formula (XVII) can be converted byacidifying to compounds of the formula (XIX)

and then converted by reacting with compounds of the formula (XIIb) tocompounds of the formula (XV). This reaction can be carried out asdescribed for the preparation of the compounds of the formula (XIV).

The compounds of the formula (XV) include in particular the compounds ofthe formulae (Ic), (Ie), (If) and (Ih) preferred according to theinvention.

The compounds of the formula (Ib)

can be prepared, for example, in a manner known per se (see alsoTerfort, Synthesis, 1992, 951-953) by reacting compounds of the formula(XXa)

or compounds of the formula (XXb)

where R¹ and R² have the definition and areas of preference specifiedunder formula (I) and R¹⁹ has the definition and areas of preferencespecified under formula (VII) initially with phosphides of the formula(XVII), thus obtaining compounds of the formula (XXIa) or compounds ofthe formula (XXIb)

and reacting the compounds of the formula (XXIa) or compounds of theformula (XXIb) with compounds of the formula (XVII) to give compounds ofthe formula (Ib).

When the radicals P(R¹³)₂ in formula (Ib) are identical, the conversioncan also be effected in one step.

The compounds of the formulae (XXIa) and (XXIb) are likewise encompassedby the invention.

Some of the compounds of the formula (XXb) are known from the literature(see, for example, Tetrahedron: Asymmetry, 2000, 11, 2899 to 2906).Further compounds of the formulae (XXa) and (XXb) can be prepared in asimilar manner to the literature. The compounds of the formula (XXb) arelikewise encompassed by the invention as particularly suitableintermediate compounds for preparing compounds of the formula (I).

The invention also encompasses transition metal complexes which containthe compounds of the formula (I) according to the invention.

Transition metal complexes are preferably those of ruthenium, osmium,cobalt, rhodium, iridium, nickel, palladium, platinum and copper,preferably those of ruthenium, rhodium, iridium, nickel, palladium,platinum and copper.

The transition metal complexes according to the invention are suitablein particular as catalysts. The invention therefore also encompassescatalysts which contain the transition metal complexes according to theinvention.

Useful catalysts are, for example, either isolated transition metalcomplexes or those transition metal complexes which are obtainable byreacting transition metal compounds and compounds of the formula (I).

Isolated transition metal complexes which contain the compounds of theformula (I) are preferably those in which the ratio of transition metalto compound of the formula (I) is 1:1.

Preference is given to the compounds according to the invention of theformula (XXIII)[(I)L¹ ₂M]  (XXIII)where (I) is a compound of the formula (I) with the definition and areasof preference specified there and

-   M is rhodium or iridium and-   L¹ is in each case a C₂-C₁₂-alkene, for example ethylene or    cyclooctene, or a nitrile, for example acetonitrile or benzonitrile    or benzyl nitrile, or-   L₂ together is a (C₄-C₁₂)-diene, for example    bicyclo[2.1.1]hepta-2,5-diene (norbornadiene) or 1,5-cyclooctadiene.

Compounds of the formula (XXIII) include:

-   [Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol)]BF₄,    [Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol)]BF₄,    [Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol)]BF₄    and    [Ir(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol)]BF₄.

Preferred transition metal complexes are those which are obtainable byreacting transition metal compounds and compounds of the formula (I).

Suitable transition metal compounds are, for example, those of theformula (XXIIa)M(An¹)_(q)  (XXIIa)where

-   M is rhodium, iridium, ruthenium, nickel, palladium, platinum or    copper and-   An¹ is chloride, bromide, acetate, nitrate, methanesulphonate,    trifluoro-methanesulphonate or acetylacetonate and-   q is 3 for rhodium, iridium and ruthenium, is 2 for nickel,    palladium and platinum, and is 1 for copper,    or transition metal compounds of the formula (XXIIb),    M(An²)_(q)L¹ ₂  (XXIIb)    where-   M is ruthenium, iridium, ruthenium, nickel, palladium, platinum or    copper and-   An² is chloride, bromide, acetate, methanesulphonate or    trifluoro-methanesulphonate, tetrafluoroborate or    hexafluorophosphate, perchlorate, hexafluoroantimonate,    tetra(bis-3,5-trifluoromethylphenyl)-borate or tetraphenylborate and-   q is 1 for rhodium and iridium, is 2 for ruthenium, nickel,    palladium and platinum, and is 1 for copper,-   L¹ is in each case a C₂-C₁₂-alkene, for example ethylene or    cyclooctene, or a nitrile, for example acetonitrile, benzonitrile or    benzyl nitrile, or-   L¹ ₂ together is a (C₄-C₁₂)-diene, for example    bicyclo[2.1.1]hepta-2,5-diene (norbornadiene) or 1,5-cyclooctadiene,    or transition metal compounds of the formula (XXIIc)    [ML²An¹ ₂]₂  (XXIIc)    where-   M is ruthenium and-   L² is an aryl radical, for example cymene, mesityl, phenyl or    cyclooctadiene, norbornadiene or methylallyl    or transition metal compounds of the formula (XXIId),    Met³ _(q)[M(An³)₄]  (XXIId)    where-   M is palladium, nickel, iridium or rhodium and-   An³ is chloride or bromide and-   Met³ is lithium, sodium, potassium, ammonium or organic ammonium and-   q is 3 for rhodium and iridium, and is 2 for nickel, palladium and    platinum,    or transition metal compounds of the formula (XXIIe),    [M(L ³)₂]An⁴  (XXIIe)    where-   M is iridium or rhodium and-   L³ is (C₄-C₁₂)-diene, for example bicyclo[2.1.1]hepta-2,5-diene    (norbornadiene) or 1,5-cyclooctadiene and-   An⁴ is a noncoordinating or weakly coordinating anion, for example    methanesulphonate, trifluoromethanesulphonate, tetrafluoroborate,    hexafluorophosphate, perchlorate, hexafluoroantimonate,    tetra(bis-3,5-trifluoromethylphenyl)-borate or tetraphenylborate.

Also suitable as transition metal compounds are, for example,Ni(1,5-cyclooctadiene)₂, Pd₂(dibenzylideneacetone)₃, Pd[PPh₃]₄,cyclopentadienyl₂Ru, Rh(acac)(CO)₂, Ir(pyridine)₂(1,5-cyclooctadiene),Cu(phenyl)Br, Cu(phenyl)Cl, Cu(phenyl)I, Cu(PPh3)₂Br, [Cu(CH₃CN)₄]BF₄and [Cu(CH₃CN)₄]PF₆ or multinuclear bridged complexes, for example[Rh(1,5-cyclooctadiene)Cl]₂, [Rh(1,5-cyclooctadiene)Br]2,[Rh(ethene)₂Cl]₂ or [Rh(cyclooctene)₂Cl]₂.

The transition metal compounds used are preferably: [Rh(cod)Cl]₂,[Rh(cod)Br]₂, [Rh(cod)₂]ClO₄, [Rh(cod)₂]BF₄, [Rh(cod)₂]PF₄,[Rh(cod)₂]ClO₆, [Rh(cod)₂]OTf, [Rh(cod)₂]BAr₄(Ar=3,5-bistrifluoromethylphenyl), [Rh(cod)₂]SbF₆, RuCl₂(cod),[(cymene)RuCl₂]₂, [(benzene)-RuCl₂]₂, [(mesityl)RuCl₂]₂,[(cymene)RuBr₂]₂, [(cymene)Rul₂]₂, [(cymene)Ru(BF₄)₂]₂,[(cymene)Ru(PF₆)₂]₂, [(cymene)Ru(BAr₄)₂]₂(Ar=3,5-bistrifluoromethylphenyl), [(cymene)Ru(SbF₆)₂]₂, [Ir(cod)Cl]₂,[Ir(cod)₂]PF₆, [Ir(cod)₂]ClO₄, [Ir(cod)₂]SbF₆, [Ir(cod)₂]BF₄,[Ir(cod)₂]OTf, [Ir(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl), RuCl₃,NiCl₃, RhCl₃, PdCl2, PdBr₂, Pd(OAc)₂, Pd₂(dibenzylideneacetone)₃,Pd(acetyl-acetonate)₂, CuOTf, CuI, CuCl, Cu(OTf)₂, CuBr, CuI, CuBr₂,CuCl₂, Cul₂, [Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)₂]ClO₄, [Rh(nbd)₂]BF₄,[Rh(nbd)₂]PF₆, [Rh(nbd)₂]OTf, [Rh(nbd)₂]BAr₄(Ar=3,5-bistrifluoro-methylphenyl), [Rh(nbd)₂]SbF₆, RuCl₂(nbd),[Ir(nbd)₂]PF₆, [Ir(nbd)₂]ClO₄, [Ir(nbd)₂]SbF₆, [Ir(nbd)₂]BF₄,[Ir(nbd)₂]OTf, [Ir(nbd)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl),Ir(pyridine)₂(nbd), [Ru(DMSO)₄Cl₂], [Ru(CH₃CN)₄Cl₂], [Ru(PhCN)₄Cl₂],[Ru(cod)C[₂]_(n), [Ru(cod)₄(methallyl)₂], [Ru(acetylacetonate)₃].

Still greater preference is given to [Rh(cod)Cl]₂, [Rh(cod)Br]₂,[Rh(cod)₂]ClO₄, [Rh(cod)₂]BF₄, [Rh(cod)₂]PF₄, [Rh(cod)₂]ClO₆,[Rh(cod)₂]OTf, [Rh(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl),[Rh(cod)₂]SbF₆, [Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)₂]ClO₄,[Rh(nbd)₂]BF₄, [Rh(nbd)₂]PF₆, [Rh(nbd)₂]OTf, [Rh(nbd)₂]BAr₄(Ar=3,5-bistrifluoromethylphenyl), [Rh(nbd)₂]SbF₆, [Ir(cod)Cl]₂,[Ir(cod)₂]PF₆, [Ir(cod)₂]ClO₄, [Ir(cod)₂]SbF₆, [Ir(cod)₂]BF₄,[Ir(cod)₂]OTf, [Ir(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl).

The amount of the transition metal compounds used may, for example, be25 to 200 mol %, based on the chiral diphosphorus compound of thegeneral formula (I) used, preferably 50 to 150 mol %, very particularlypreferably 75 to 125 mol % and even more preferably 100 to 115 mol %.

The catalysts which contain the transition metal complexes according tothe invention are suitable in particular for use in a process forpreparing stereoisomerically enriched, preferably enantiomericallyenriched, compounds.

Preference is given to using the catalysts for asymmetric 1,4-additions,asymmetric hydroformylations, asymmetric hydrocyanations, asymmetricHeck reactions and asymmetric hydrogenations, more preferably forasymmetric hydrogenations.

Preferred asymmetric hydrogenations are, for example, hydrogenations ofprochiral C═C bonds for example prochiral enamines, olefins, enolethers, C═O bonds, for example prochiral ketones, and C═N bonds, forexample prochiral imines. Particularly preferred asymmetrichydrogenations are hydrogenations of prochiral C═C bonds, for exampleprochiral enamines, olefins, and C═N bonds, for example prochiralimines.

The invention therefore also encompasses a process for preparingstereoisomerically enriched, preferably enantiomerically enriched,compounds by catalytic hydrogenation of olefins, enamines, enamides,imines or ketones, which is characterized in that the catalysts used arethose which contain the transition metal complexes of compounds of theformula (I) as defined there.

The amount of the transition metal compound or of the transition metalcomplex used may, for example, be 0.001 to 5 mol %, based on thesubstrate used, preferably 0.001 to 0.5 mol %, very particularlypreferably 0.001 to 0.1 mol % and even more preferably 0.001 to 0.008mol %.

In a preferred embodiment, asymmetric hydrogenations can be carried out,for example, in such a manner that the catalyst is obtained for atransition metal compound and compound of the formula (I), optionally ina suitable solvent, the substrate is added and the reaction mixture isplaced under hydrogen pressure at room temperature.

The metal compounds used for asymmetric hydrogenations are particularlypreferably those of the general formula (XXIV)[M(L³)₂]An⁴  (XXIV)where M is rhodium or iridium, and L³ and An are as defined above, ordinuclear complexes, for example [Rh(1,5-cyclooctadiene)Cl]₂,[Rh(1,5-cyclooctadiene)Br]₂, [Rh(ethene)₂Cl]₂, [Rh(cyclooctene)₂Cl]₂.

Particularly preferred metal compounds for asymmetric hydrogenations are[Rh(cod)₂]OTf, [Rh(cod)₂]BF₄, [Rh(cod)₂]PF₆, [Rh(nbd)₂]PF₆,[Rh(nbd)₂]BF₄, and [Rh(norbornadiene)₂]OTf, [Ir(cod)₂]BF₄ and [Ir(cod)₂PF₆].

In a particularly preferred embodiment, transition metal compound andcompound of the formula (I) are dissolved in degassed solvent in abaked-out glass autoclave. The mixture is stirred for approx. 5 min andthe substrate is subsequently added in degassed solvent. After setting aparticular temperature, hydrogenation is effected under elevated H₂pressure.

Suitable solvents for asymmetric catalysis are, for example, chlorinatedalkanes such as methyl chloride, short-chain C₁-C₆-alcohols, e.g.methanol, isopropanol or ethanol, aromatic hydrocarbons, e.g. toluene orbenzene, ketones, e.g. acetone, or carboxylic esters, e.g. ethylacetate.

The asymmetric catalysis is advantageously carried out at a temperatureof −20° C. to 200° C., preferably 0 to 100° C. and more preferably 20°to 70° C.

The hydrogen pressure may, for example, be 0.1 to 200 bar, preferably0.5 to 100 bar and more preferably 1 to 70 bar.

The catalysts according to the invention are suitable in particular in aprocess for preparing stereoisomerically enriched, preferablyenantiomerically enriched, active ingredients in pharmaceuticals andagrochemicals, or intermediates of these two classes.

The advantage of the present invention is that the ligands can beprepared in an efficient manner and their electronic and stericproperties are variable to a high degree starting from readily availablereactants. The ligands according to the invention and their transitionmetal complexes, especially in asymmetric hydrogenations of C═C bondsand imines, also exhibit turnover frequencies (TOFS) of over 1000/h,which are well above those of comparable systems.

The invention is further illustrated but is not intended to be limitedby the following examples in which all parts and percentages are byweight unless otherwise specified.

EXAMPLES Example 1

1,6-Di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol (B1): a mixture of2.35 g (14.33 mmol) of 2,5-anhydro-D-mannitol and 8.79 g (31.53 mmol) oftriphenylmethyl chloride in 38 ml of pyridine was stirred at 100° C. for12 hours. After cooling, the mixture was diluted with CH₂Cl₂, and washedwith aq.HCl (0.78 mol/l), the organic phase was dried over Na₂SO₄ andthe solvent was subsequently removed under reduced pressure. The crudeproduct was purified by means of column chromatography (hexane/ethylacetate 2:1). Yield: 5.57 g (60% of theory).

¹H NMR (400 MHz, CHCl₃) δ, 7.60-7.03 (m, 15H, Ph), 4.12 (m, 1H, H-2),3.96 (m, 1H, H-3), 3.45 (dd, 1H, J_(6,2)=3.9 Hz, J_(6,6′)=10.2 Hz, H-6),3.39 (sa, 1H, OH), 3.22 (dd, 1H, J_(6′,2)=4.2 Hz, J_(6′,6)=10.2 Hz,H-6′); ¹³C NMR (100.6 MHz) δ, 143.31.-127.02 (Ph), 87.31 (C(Ph)₃), 83.63(C-2), 79.45 (C-3), 64.79 (C-6).

Example 2

1,6-Di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol (B2): 3 ml(11.66 mmol) of tert-butyidiphenylsilyl chloride (TBDMPSCI) were addeddropwise at 0° C. to a solution of 0.87 g (5.3 mmol) of2,5-anhydro-D-mannitol and 1.5 g (22.28 mmol) of imidazole in 12 ml ofanhydrous DMF. The mixture was heated to room temperature and stirredfor a further 25 hours, and the solvent was subsequently removed underreduced pressure. The mixture was diluted with CH₂Cl₂ and washed withwater, the organic phase was dried over Na₂SO₄ and the solvent wassubsequently removed under reduced pressure. The crude product waspurified by means of column chromatography (hexane/ethyl acetate 4:1).Yield 1.36 g (40% of theory).

¹H NMR (400 MHz, CDCl₃) 8, 7.81-7.30 (m, 10H, Ph); 4.25 (m, 1H, H-3);4.17 (m, 1H, H-2); 4.04 (d, 1H, OH); 3.86 (dd, 1H, J_(6,2)=3.7 Hz,J_(6,6′)=11.1 Hz, H-6); 3.75 (dd, 1H, J_(6′,2)=3.2 Hz, J_(6,6′)=11.1 Hz,H-6′); 1.07 (s, 9H, C(CH ₃)₃); ¹³C NMR (100.6 MHz) δ, 136.10-126.99(Ph), 87.09 (C-2), 79.71 (C-3), 65.52 (C-6), 26.73 (C(CH₃)₃), 19.02(C(CH₃)₃).

Example 3

1,6-Di-O-(p-toluenesulphonyl)-2,5-anhydro-D-mannitol (B3): 5.33 g(27.945 mmol) of p-toluenesulphonyl chloride were added at 0° C. to asolution of 2.16 g (13.15 mmol) of 2,5-anhydro-D-mannitol in 88 ml ofpyridine. The mixture was heated to room temperature and stirred for afurther 24 hours. The reaction was hydrolysed using ice-water andextracted using CH₂Cl₂, and the combined organic phases were washed with3N HCl and NaCl. After drying over MgSO₄, the solvent was subsequentlyremoved under reduced pressure. The crude product was purified by meansof column chromatography (hexane/ethyl acetate 1:2).

Yield: 3.00 g (48% of theory).

¹H NMR (400 MHz, CDCl₃) δ, 7.82-7.31 (m, 4H, Ph); 4.2-3.9 (m, 4H, H-2,H-3, H-6, H-6′); 2.44 (s, 3H, CH₃); ¹³C NMR (100.6 MHz, CDCl₃) δ,145.05-126.86 (Ph), 80.42 (C-2), 77.32 (C-3), 68.84 (C-6), 21.81 (CH₃).

Example 4

1,6-Dideoxy-2,5-anhydro-D-mannitol (B4): 0.86 g (22.66 mmol) of LiAlH₄was added to a solution of 3.60 g (7.63 mmol) of B3 in 20 ml ofanhydrous THF and stirred at reflux for 2 hours. After cooling,Arberlite® IR-120(plus) was added and stirring was continued untilhydrogen evolution had ended. The mixture was filtered through Celite®and the solvent was subsequently removed under reduced pressure. Thecrude product was purified by means of column chromatography(CH₂Cl₂/MeOH=12:1).

Yield: 0.84 g (84% of theory).

¹H NMR (400 MHz, CDCl₃) δ, 3.84 (m, 1H, H-2), 3.64 (m, 1H, H-3), 1.27(d, 1H, J_(6,2)=6 Hz, H-6); ¹³C NMR (100.6 MHz; CDCl₃)δ, 84.18 (C-2),79.29 (C-3), 19.61 (C-6).

Example 5

2,3-bis-O-(Diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol(B5). 0.61 ml (4.4 mmol) of anhydrous Et₃N was added to a solution of0.63 g (1.0 mmol) of B1 in 5 ml of anhydrous, degassed CH₂Cl₂. At −15°C., a solution of 0.39 ml (2.2 mmol) of diphenylchlorophosphine in 3 mlof CH₂Cl₂ was slowly added dropwise. After stirring at −15° C. for 15minutes, ethyl ether was added, the salts were filtered off throughCelite® and the solvent was subsequently removed under reduced pressure.The crude product was purified by means of column chromatography underargon (hexane/ethyl acetate 15:1). Yield 0.51 g (51% of theory).

[α]_(D)=+0.4 (c 1.04, CHCl₃); ¹H NMR (400 MHz, CHCl₃) δ, 760.-7.02 (m,25H, Ph), 4.62 (m, 1H, H-3), 4.29 (m, 1H, H-2), 3.198 (d, 2H,J_(6,2)=5.6 Hz, H-6, H-6′); ¹³C NMR (100.6 MHz) δ, 144.33-127.06 (Ph),86.901 (C(Ph)₃), 86.14 (m, C-3), 83.51 (m, C-2), 64.25 (s, C-6); ³¹P NMR(161.974 MHz, CDCl₃) δ, 116.23 (s). Anal calcd for C₆₈H₅₈O₅P₂: C, 80.29;H, 5.74; found C, 79.99; H, 5.72.

Example 6

2,3-bis-O-(Diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol(B6): This product was prepared from B2 at −25° C. in a similar mannerto Example 5. Yield: 0.816 g (50%), white oil.

[α]_(D)=+9.9 (c 1.8, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ, 7.81-7.02 (m,20H, Ph), 4.88 (m, 1H, H-3), 4.18 (m, 1H, H-2), 3.76 (dd, 1H, JH-6),3.63 (d, 1H, H-6′); 1.02 (s, 9H, C(CH ₃)₃); ¹³C NMR (100.6 MHz, CDCl₃)δ, 144.02-126.10 (Ph), 86.14 (m, C-3), 83.51 (m, C-2), 64.25 (s, C-6),26.79 (C(CH₃)₃), 19.26 (C(CH₃)₃); ³¹P NMR (161.974 MHz, CDCl₃) δ, 116.23(s).

Anal calcd for C₆₂H₆₆O₅P₂Si₂: C, 73.78; H, 6.59; found C, 73.65; H,6.57.

Example 7

2,3-bis-O-(Diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol (B7):This product was prepared from B4 in a similar manner to Example 5.Yield: 58% of theory.

[α]_(D)=−20.4 (c 1.04, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ, 7.60-7.02 (m,10H, Ph), 4.26 (m, 1H, H-3), 4.12 (m, 1H, H-2), 1.21 (d, 3H, J_(6,2)=6.4Hz, H-6); ¹³C NMR (100.6 MHz, CDCl₃) δ, 142.12-127.08 (Ph), 90.74 (m,C-2), 78.35 (m, C-3), 19.15 (s, C-6); ³¹P NMR (161.974 MHz, CDCl₃) δ,114.39 (s). Anal calcd for C₃₀H₃₀O₃P₂: C, 71.99; H, 6.04; found C,72.22; H, 6.06.

Example 8

1,6-di-O(Triphenylmethyl)-2,5-anhydro-L-iditol (B8): This product wasprepared starting from 2,5-anhydro-L-iditol in a similar manner toExample 1.

¹H NMR (400 MHz, CHCl₃) δ, 7.60-7.02 (m, 15H, Ph), 4.42 (m, 1H, H-2),4.25 (m, 1H, H-3), 3.48 (dd, 1H, J_(6,2)=5.4 Hz, J_(6,6′)=9.6 Hz, H-6),3.40 (dd, 1H, J_(6′,2)=3.8 Hz, J_(6′,6)=9.8 Hz, H-6′); 3.24 (sa, 1H,OH), ¹³C NMR (100.6 MHz) δ, 143.20.-127.01 (Ph), 87.20 (C(Ph)₃), 78.78(C-2), 78.65 (C-3), 62.78 (C-6).

Example 9

1,6-di-O-(tert-Butyldiphenylsilyl)-2,5-anhydro-L-iditol (B9): Thisproduct was prepared starting from 2,5-anhydro-L-iditol in a similarmanner to Example 2.

¹H NMR (400 MHz, CDCl₃) δ, 7.81-7.32 (m, 10H, Ph); 4.26 (m, 1H, H-2);4.38 (m, 1H, H-3); 4.07 (d, 1H, J_(6,2)=4.4 Hz, J_(6,6′)=10.8 Hz, H-6);4.05 (d, 1H, J_(6′,2)=3.2 Hz, J_(6′,6)=10.8 Hz, H-6′); 3.99 (d, 1H, OH);1.06 (s, 9H, C(CH ₃)₃); ¹³C NMR (100.6 MHz) δ, 135.52-127.6 (Ph), 79.74(C-2), 78.95 (C-3), 63.74 (C-6), 26.79 (C(CH₃)₃), 19.19 (C(CH₃)₃).

Example 10

1,6-di-O-(p-Toluenesulphonyl)-2,5-anhydro-L-iditol (B10)

This product was prepared starting from 2,5-anhydro-L-iditol in asimilar manner to Example 3.

¹H NMR (400 MHz, CDCl₃) δ, 7.83-7.21 (m, 4H, Ph); 4.42-3.91 (m, 5H, H-2,H-3, H-6, H-6′, OH); 2.44 (s, 3H, CH₃); ¹³C NMR (100.6 MHz, CDCl₃) δ,145.11-127.83 (Ph), 77.83 (C-2), 76.54 (C-3), 67.22 (C-6), 21.82 (CH₃).

Example 11 1,6-Dideoxy-2,5-anhydro-L-iditol (B11)

This product was prepared starting from B10 in a similar manner toExample 4.

¹H NMR (400 MHz, CDCl₃) δ, 4.22 (m, 1H, H-2), 3.90 (m, 1H, H-3), 1.18(d, 1H, J_(6,2)=6.6 Hz, H-6); ¹³C NMR (100.6 MHz; CDCl₃) δ, 79.66 (C-2),77.30 (C-3), 14.68 (C-6).

Example 122,3-bis-O-(Diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-L-iditol(B12)

This product was prepared starting from B8 in a similar manner toExample 5.

¹H NMR (400 MHz, CHCl₃) δ, 750.-7.51 (m, 25H, Ph), 4.30 (m, 1H, H-2),4.37 (m, 1H, H-3), 3.48 (dd, 1H, J_(6,2)=9.4 Hz, J_(6,6′)=9.4 Hz, H-6);3.18 (dd, 1H, J_(6′,2)=5.8 Hz, J_(6′,6)=9.4 Hz, H-6′) ¹³C NMR (100.6MHz) 8, 143.91-126.62 (Ph), 86.77 (C(Ph)₃), 82.64 (m, C-3), 79.654 (d,C-2), 62.82 (s, C-6); ³¹P NMR (161.974 MHz, CDCl₃) δ, 114.12 (s).

Example 132,3-bis-O-(Diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-L-iditol(B13)

This product was prepared starting from B9 in a similar manner toExample 5.

¹H NMR (400 MHz, CDCl₃) δ, 7.81-7.09 (m, 20H, Ph), 4.51 (m, 1H, H-3),4.21 (m, 1H, H-2), 3.85 (dd, 1H, J_(6,2)=7.4 Hz, J_(6,6′)=10.0 Hz H-6),3.72 (dd, 1H, J_(6′,2)=5.8 Hz, J_(6′,6)=10.0 Hz, H-6′), 0.94 (s, 9H,C(CH ₃)₃); ¹³C NMR (100.6 MHz, CDCl₃) δ, 135.51-127.43 (Ph), 83.09 (m,C-3), 80.68 (d, C-2), 61.73 (s, C-6), 26.92 (C(CH₃)₃), 19.25 (C(CH₃)₃);³¹P NMR (161.974 MHz, CDCl₃) δ, 115.74 (s).

Example 142,3-bis-O-(Diphenylphosphino)-1,6-dideoxy-2,5-anhydro-L-iditol (B14)

This product was prepared starting from B11 in a similar manner toExample 5.

¹H NMR (400 MHz, CDCl₃) δ, 7.63-7.21 (m, 10H, Ph), 4.32 (m, 1H, H-2),4.23 (m, 1H, H-3), 1.20 (d, 3H, J_(6,2)=6.4 Hz, H-6); ¹³C NMR (100.6MHz, CDCl₃) δ, 142.05-127.99 (Ph), 84.97 (m, C-3), 76.02 (m, C-2), 15.18(s, C-6); ³¹P NMR (161.974 MHz, CDCl₃) δ, 114.05 (s).

Example 15

[Rh(cod)(B5)]BF₄ (B15): 0.030 g (0.073 mmol) of [Rh(cod)₂]BF₄ wasdissolved in 10 ml of CH₂Cl₂. A solution of 0.090 g (0.088 mmol) ofcompound B5 in 3 ml CH₂Cl₂ was added to the solution and the resultingsolution was stirred for 30 min. The solvent was removed under reducedpressure and the crude product was washed with anhydrous hexane and withethyl ether. Yield: 0.042 g (43% of theory).

[α]_(D)=+119.41 (c 1.05, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ, 7.60-7.02(m, 25H, Ph), 5.36 (m, 1H, H-3), 4.70 (m, 2H, CH(cod)); 4.47 (m, 1H,H-2), 3.58 (dd, 1H, J_(6,2)=2.8 Hz, J_(6,6′)=10.8 Hz, H-6), 3.18 (dd,1H, J_(6,2)=3.2 Hz, J_(6,6′)=10.8 Hz, H-6′); 2.42-2.00 (m, 4H,CH₂(cod)); ¹³C NMR (100.6 MHz) δ, 144.10-126.05 (Ph, cod), 87.00(C(Ph)₃), 82.67 (s, C-3), 82.45 (m, C-2), 63.33 (s, C-6); ³¹P NMR(161.974 MHz, CDCl₃) δ, 122.61 (d, J_(P,Rh)=166.18 Hz)).

Example 16

[Rh(cod)(B6)]BF₄ (B16): This complex was prepared from B6 in a similarmanner to Example 15. Yield: 68% of theory.

[α]_(D)=(c, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ, 7.82-7.21 (m, 20H, Ph),5.24 (m, 1H, H-3), 4.77 (m, 1H, CH(cod)); 4.67 (m, 1H, CH(cod)); 4.19(m, 1H, H-2), 3.85 (dd, 1H, J_(6,2)=2.4 Hz, J_(6,6′)=11.6 Hz, H-6), 3.69(dd, 1H, J_(6′, 2)=3.2 Hz, J_(6,6′)=11.6 Hz, H-6′); 2.41-2.20 (m, 4H,CH₂(cod)); 1.04 (s, 9H, C(CH₃)₃); ¹³C NMR (100.6 MHz, CDCl₃) δ,134.10-126.07 (Ph, cod), 82.53 (m, C-2), 81.23 (s, C-3), 63.13 (s, C-6),26.95 (C(CH₃)₃), 19.44 (C(CH₃)₃); ³¹P NMR (161.974 MHz, CDCl₃) δ,125.136 (d, J_(P,Rh)=167.97 Hz).

Example 17

[Rh(cod)(B7)]BF₄ (B17): This complex was prepared starting from B7 in asimilar manner to Example 15. Yield: 55% of theory.

¹H NMR (400 MHz, CDCl₃) δ, 7.81-7.42 (m, 10H, Ph), 4.73 (m, 1H,CH(cod)); 4.64 (m, 1H, CH(cod)); 4.39 (m, 1H, H-3), 3.91 (m, 1H, H-2),);2.61-2.20 (m, 4H, CH₂(cod)); 1.13 (d, 3H, J_(6,2)=6.0 Hz, H-6); ¹³C NMR(100.6 MHz, CDCl₃) δ, 133.15-128.03 (Ph, cod), 85.76 (s, C-3), 75.68 (m,C-2), 18.64 (s, C-6); ³¹P NMR (161.974 MHz, CDCl₃) δ, 127.39 (d,J_(P,Rh)=169.42 Hz).

Example 18

[Ir(cod)(B6)]BF₄ (B18): A solution of 102 mg (0.1 mmol) of compound B6in 2 ml of CH₂Cl₂ was added dropwise to a solution cooled to −80° C. of40 mg (0.08 mmol) of [Ir(cod)₂]BF₄ in 2 ml CH₂Cl₂. The resulting yellowsolution was heated to 0° C. and stirred for a further 15 minutes. Thesolvent was partly removed under reduced pressure, 30 ml of ethyl etherwere added and the solids were filtered off and washed. Yield: 98.6 mg,86% of theory.

¹H NMR (400 MHz, CDCl₃) δ, 7.44-7.24 (m, 50H, CH arom), 5.35 (m, 2H,CH), 5.17 (m, 1H, CH); 4.52 (m, 2H, CH); 4.41 (m, 4H, CH₂); 3.60 (dd,J=2.6 Hz, J=10.4 Hz, 2H, CH₂), 3.21 (dd, J=2.6 Hz, J=10.4 Hz, 2H, CH₂),2.42 (m, 2H, cod), 2.21 (m, 2H,), 2.06 (m, 2H), 1.67 (m, 2H). ¹³C NMR(100.6 MHz) δ, 143.6 (C arom.), 132.4 (s, arom); 32.0 (s, arom); 131.7(t, arom.), 131.2 (t, arom.), 129.1 (m, arom.), 128.7 (m, arom.), 128.68(s, CH arom.), 128.1 (s, CH arom.), 127.4 (s, CH arom), 95.5 (s, CH),83.3 (s, CH), 87.2 (s, C), 83.1 (s, CH), 82.4 (s, CH), 63.7 (CH₂), 31.3(s, CH₂), 31.1 (s, CH₂). ³¹P NMR (161.9 MHz, CDCl₃) δ, 104.6.

Examples 19-41

Rhodium-Catalysed Hydrogenation of Enamides and Methyl Itaconate

In a glass autoclave, 6.1 mg (0.015 mmol) of [Rh(cod)₂]BF₄ weredissolved in 15 ml of degassed CH₂Cl₂, 0.016 mmol of ligand and 1 mmolof substrate were added under nitrogen and hydrogenation was effected atroom temperature and 1 atm of hydrogen pressure. Conversion and ee weredetermined by gas chromatography.Ligands:

Substrates:

The results of the hydrogenations are compiled in Table 1. TABLE 1 Exam-Sub- Solution t Subst/Rh % % ee ples strate Ligand (ml) (min) (mol)conv. (R/S) 19 S1 B5 CH₂Cl₂ 15 5 100 100 62(R) 20 S1 B5 CH₂Cl₂ 15 35 50093 67(R) 21 S1 B5 CH₂Cl₂ 15 10 250 100 65(R) 22 S1 B5 MeOH 15 15 500 6373(R) 23 S1 B5 acetone 15 15 500 99 75(R) 24 S1 B5 THF 15 15 500 3663(R) 25 S1 B5 toluene/ 15 500 59 65(R) MeOH 15 26 S1 B6 CH₂Cl₂ 15 5 10095 70(R) 27 S1 B6 CH₂Cl₂/ 5 100 100 85(R) acetone 2:13 28 S1 B6 CH₂Cl₂/5 100 100 87(R) acetone 2:13 29 S1 B6 CH₂Cl₂/ 15 100 100 90(R) acetone2:13 30 S1 B7 CH₂Cl₂ 15 5 100 100 73(R) 31 S1 B7 CH₂Cl₂/ 5 100 100 79(R)acetone 2:13 32 S2 B5 CH₂Cl₂ 15 10 100 91 59(R) 33 S2 B5 Acetone 15 10100 91 73(R) 34 S2 B6 CH₂Cl₂ 15 5 100 98 73(R) 35 S2 B6 CH₂Cl₂/ 5 100 9680(R) acetone 2:13 36 S2 B7 CH₂Cl₂ 15 5 100 100 72(R) 37 S2 B7 CH₂Cl₂/ 5100 100 75(R) acetone 2:13 38 S3 B5 CH₂Cl₂ 15 15 100 100 48(S) 39 S3 B5acetone 15 60 100 33 35(S) 40 S3 B6 CH₂Cl₂ 15 15 100 96 48(S) 41 S3 B7CH₂Cl₂ 15 5 100 96 53(S)Preparation of Phosphine Chlorides:

Examples 42-45

Bis-(2,4-dimethylphenyl)chlorophosphine (B42): A solution of 2.92 ml(2161 mmol) of 4-bromo-1,3-dimethylbenzene in 3 ml of Et₂O were added at0° C. to a suspension of 0.5 g (20.56 mmol) of magnesium turnings in 7ml of THF and 7 ml of Et₂O and also a crystal of iodine. The mixture washeated to room temperature, stirred further overnight and slowly addeddropwise at 0° C. to a solution of 1.5 ml (10.31 mmol) of Et₂NPCl₂ in 8ml of THF. The mixture was heated to room temperature and the solventwas subsequently removed under reduced pressure. After adding 60 ml ofhexane, the mixture was filtered through Celite under argon and admixedwith hydrogen chloride for 1 hour. After degassing, the resulting solidswere filtered off under argon and dried. Yield: 1.4 g (58.3% of theory).¹H NMR (400 MHz, CDCl₃) δ, 7.40 (d, Jmeta=4.5 Hz, 2H, arom.), 7.2 (m,4H, arom.), 2.5 (d, J_(PH)=2.0 Hz, 6H, CH₃), 2.4 (s, 6H, CH₃). ³¹P NMR(161.974 MHz, CDCl₃) δ, 75.6.

Example 43

Bis-(3,5-dimethylphenyl)chlorophosphine (B43): This product was preparedstarting from 5-bromo-1,3-dimethylbenzene in a similar manner to Example42. Yield: 47.2% of theory. ¹H NMR (400 MHz, CDCl₃) δ, 7.2 (d, 4H,arom.), 7.01 (s, 2H, arom.), 2.37 (s, 12H, CH₃). ³¹P NMR (161.974 MHz,CDCl₃) δ, 83.7.

Example 44

Bis-(4-methoxyphenyl)chlorophosphine (B44): This product was preparedstarting from 1-bromo-4-methoxybenzene in a similar manner to Example42. Yield 45% of theory. ¹H NMR (400 MHz, CDCl₃) δ, 7.48 (t, Jorto=8.4Hz, J_(PH)=8.4 Hz, 4H, arom.), 6.88 (d, Jorto=8.4 Hz, 4H, arom.), 3.75(s, 6H, CH₃O). ³¹P NMR (161.974 MHz, CDCl₃) δ, 84.2.

Example 45

Bis-(4-trifluoromethylphenyl)chlorophosphine (B45): This product wasprepared starting from 1-bromo-4-(trifluoromethyl)benzene in a similarmanner to Example 42. Yield 66% of theory. ¹H NMR (400 MHz, CDCl₃) δ,7.33 (m, 8H, arom.). ³¹P NMR (161.9 MHz, CDCl₃) δ, 76.3.

Preparation of Aminophosphines:

Exampl 46

(Diethylamino)-bis(2,4-dimethylphenyl)phosphine (B46): A solution of2.92 ml (21.61 mmol) of 4-bromo-1,3-dimethylbenzene in 3 ml of Et₂O wereadded at 0° C. to a suspension of 0.5 g (20.56 mmol) of magnesiumturnings in 7 ml of THF and 7 ml of Et₂O and also a crystal of iodine.The mixture was heated to room temperature, stirred further overnightand slowly added dropwise at 0° C. to a solution of 1.5 ml (10.31 mmol)of Et₂NPCl₂ in 8 ml of THF. The mixture was heated to 5-10° C., stirredfor a further 2 hours and the solvent was subsequently removed underreduced pressure. After adding 60 ml of hexane, the mixture was filteredthrough Celite under argon and the solvent was subsequently removedunder reduced pressure. Yield: 1.37 g (59% of theory). ¹H NMR (400 MHz,CDCl₃) δ, 6.9 (m, 6H), 3.03 (m, 4H, CH₂), 2.20 (s, 12H, CH₃), 0.81 (t,³J=7.0 Hz, 6H, CH₃) ³¹P NMR (161.9 MHz, CDCl₃) δ, 47.8.

Example 47

(Diethylamino)bis(3,5-dimethylphenyl)phosphine (B47): This product wasprepared starting from 5-bromo-1,3-dimethylbenzene in a similar mannerto Example 46. Yield 56.8% of theory. ¹H NMR (400 MHz, CDCl₃) δ, 6.90(d, 4H, arom.), 6.76 (s, 2H, arom.), 2.95 (m, 4H, CH₂), 2.11 (s, 12H,CH₃), 0.80 (t, ³J=7.0 Hz, 6H, CH₃). ³¹P NMR (161.9 MHz, CDCl₃) δ, 61.6.

Example 48

(Diethylamino)bis(4-methoxyphenyl)phosphine (B48): This product wasprepared starting from 1-bromo-4-methoxybenzene in a similar manner toExample 46. Yield: 57.2% of theory. ¹H NMR (400 MHz, CDCl₃) δ, 7.48 (dd,Joito=8.8 Hz, J_(PH)=6.4 Hz, 4H, arom.), 6.88 (m, 4H, arom.), 3.81 (s,6H, CH₃O), 3.06 (q, ³J=7.2 Hz, 2H, CH₂), 0.96 (t, ³J=7.2 Hz, ³H, CH₃).³¹P NMR (161.9 MHz, CDCl₃) δ, 59.5.

Example 49

(Diethylamino)bis(4-trifluoromethylphenyl)phosphine (B49): This productwas prepared starting from 1-bromo-4-(trifluoromethyl)benzene in asimilar manner to Example 46. Yield: 61.4% of theory. ¹H NMR (400 MHz,CDCl₃) δ, 7.39 (m, 8H, arom.), 2.92 (m, 4H, CH₂), 0.82 (t, ³J=7.0 Hz,3H, CH₃). ³¹P NMR (161.9 MHz, CDCl₃) δ, 61.5.

Preparation of Biphosphorus Compounds:

Example 502,3-bis-O-(Di(4-methoxyphenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol(B50)

A mixture of 100 mg (0.156 mmol) of1,6-di-O-(tert-butyidiphenylsilyl-2,5-anhydro-D-mannitol (B2) and 109 mg(0.343 mmol) of diethylaminobis(p-methoxybenzene)phosphine (B48) in 2.2ml of anhydrous toluene was stirred at 112° C. overnight. After cooling,the solvent was removed under reduced pressure and the crude product waspurified by means of column chromatography. Yield: 40 mg (22.7% oftheory). ¹H NMR (400 MHz, C₆D₆) δ, 7.93 (m, 8H, arom.), 7.67 (m, 8H,arom.), 7.26 (m, 12H, arom.), 6.84 (m, 8H, arom.), 5.38 (dd, J=7.9 Hz,J=4 Hz, 2H, CH), 4.59 (m, 2H, CH), 4.09 (dd, J=10.9 Hz, J=4.2 Hz, 2H,CH₂), 3.99 (dd, J=10.9 Hz, J=4.2 Hz, 2H, CH₂), 3.37 (s, 6H, CH₃O), 3.35(s, 6H, CH₃O), 1.32 (s, 9H, CH₃), 1.27 (s, 9H, CH₃). ³¹P NMR (161.9 MHz,C₆D₆) δ, 116.3.

Example 512,3-bis-O-(Di((4-trifluoromethyl)phenyl)phosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol(B51)

This product was prepared starting from1,6-di-O-(tert-butyldiphenylsilyl-2,5-anhydro-D-mannitol (B2) and(diethylamino)bis(4-trifluoromethylphenyl)phosphine (B49) in a similarmanner to Example 50.

Yield: 40 mg (28% of theory). ¹H NMR (400 MHz, C₆D₆) δ, 7.9 (m, 2H,arom.), 7.85 (m, 4H, arom.), 7.74 (m, 2H, arom.), 7.40-7.29 (m, 26H,arom.), 7.0 (m, 2H, arom), 5.36 (m, 2H, CH), 4.41 (m, 2H, CH), 4.02 (dd,J=11.4 Hz, J=3.5 Hz, 2H, CH₂), 3.79 (dd, J=1.4 Hz, J=3.5 Hz, 2H, CH₂),1.28 (s, 9H, CH₃). ³¹P NMR δ, (161.9 MHz, C₆D₆) 111.5.

Example 522-O-(Di(2,4-dimethylphenyl)phosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol(B52)

A solution of 337 mg (1.219 mmol) ofbis-(2,4-dimethylphenyl)-chlorophosphine (B46) in 2 ml of anhydrous THFwas added to a solution of 300 mg (0.468 mmol) of1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol (B2) and 0.26ml of anhydrous Et₃N (1.86 mmol), and stirred at room temperatureovernight. After adding ethyl ether, the mixture was filtered throughCelite, solvent removed under reduced pressure and the crude productpurified by means of column chromatography. Yield: 180 mg (45% oftheory). ¹H NMR (400 MHz, CDCl₃) 8, 7.59-6.87 (m, 26H, arom.), 4.47 (m,1H, CH), 4.31 (m, 1H, CH), 3.99 (m, 2H, CH), 3.69 (m, 3H, CH₂), 3.54(dd, 1H, CH₂), 2.79 (s, OH), 2.30 (s, 3H, CH₃), 2.17 (s, 3H, CH₃), 2.11(s, 3H, CH₃), 2.06 (s, 3H, CH₃), 0.96 (s, 9H, CH₃), 0.94 (s, 9H, CH₃).¹³C NMR (75.4 MHz, CDCl₃) δ, 138.1-127.6 (CH, C, arom.), 86.0(²J_(C-P)=18 Hz, CH), 84.9 (CH), 83.9 (³J_(C-P)=6.13 Hz, CH), 78.0(²J_(C-P)=4.5 Hz, CH CH), 64.7 (CH₂), 64.1 (CH₂), 27.1 (CH₃), 27.0(CH₃), 21.4 (C), 20.5 (d, ³J=48.4 Hz, CH₃), 20.3 (d, ³J=48.4 Hz, CH₃),19.6 (s, CH₃), 19.5 (s, CH₃). ³¹P NMR (161.9 MHz, CDCl₃) δ, 102.9.

Example 532-O-(2,4-dimethylphenylphosphino)-3-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol(B53)

A solution of 0.0125 ml (0.066 mmol) of chlorodiphenylphosphine wasadded to a solution of 58 mg (0.06 mmol) of2-O-(2,4-dimethylphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol(B52) and 0.032 ml (0.23 mmol) of anhydrous Et₃N in 0.5 ml of anhydrousTHF. The mixture was heated to room temperature and stirred furtherovernight. After adding degassed, anhydrous hexane, the mixture wasfiltered through Celite, the solvent removed under reduced pressure andthe crude product purified by means of column chromatography. Yield 29.4mg (45.9% of theory). ¹H NMR (400 MHz, CDCl₃) δ, 7.67-6.91 (m, 36H,arom.), 4.8 (m, 2H, CHx2), 4.15 (m, 2H, CHx2), 3.73 (m, 2H, CH₂), 3.59(m, 2H, CH₂), 2.25 (s, 3H, CH₃), 2.23 (s, 3H, CH₃), 2.19 (s, 3H, CH₃),2.14 (s, 3H, CH₃), 1.1 (s, 9H, CH₃), 1 (d, 9H, CH₃). ³¹P NMR (161.9 MHz,C₆D₆) δ, 114.1, 102.7.

Example 542-O-(2,4-Dimethylphenylphosphino)-3-O-(4,8-di-tert-butyl-2,10-dimethyl-12H-dibenzo[δ,γ][1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol(B54)

A solution of 100 mg (0.52 mmol) of4,8-di-tert-butyl-6-chloro-2,10-dimethyl-12h-dibenzo[δ,γ][1,3,2]dioxaphosphocineand 0.100 ml (1.23 mmol) of anhydrous pyridine in 1 ml of anhydroustoluene was added dropwise at 0° C. to a solution of 178 mg (0.202 mmol)of2-O-(2,4-dimethylphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol(B52) and 0.100 ml (1.23 mmol) of anhydrous pyridine in 1 ml ofanhydrous toluene. The mixture was heated to room temperature andstirred further overnight. After adding degassed, anhydrous hexane, themixture was filtered through Celite, the solvent removed under reducedpressure and the crude product purified by means of columnchromatography. Yield 100 mg (39.6% of theory). ¹H NMR (400 MHz, C₆D₆)δ, 7.97-6.38 (m, 30H, arom.), 5.50 (m, 1H, CH), 5.21 (m, 1H, CH), 4.83(m, 1H, CH), 4.53 (d, J=110.4 Hz, 1H, CH₂), 4.50 (m, 3H, CH, CH₂), 4.39(dd, 1H, J=10.8 Hz, J=5.59 Hz, CH₂), 4.15 (dd, 1H, J=10.8 Hz, J=5.59 Hz,CH₂), 3.3 (d, J=10.4 Hz, 1H, CH₂), 2.59 (s, 3H, CH₃), 2.51 (s, 3H, CH3),2.15 (s, 3H, CH₃), 2.12 (s, 6H, CH₃), 2.1 (s, 3H, CH₃), 1.54 (s, 9H,CH₃), 1.53 (s, 9H, CH₃), 1.36 (s, 9H, CH₃), 1.32 (s, 9H, CH₃) ³¹P NMR(161.9 MHz, C₆D₆) δ, 128.8, 103.6.

Example 552-O-(2,4-Dimethylphnylphosphino)-3-O-(2,10-dimethyl-4,8-bis(1-methylcyclohexyl)-12H-dibenzo[δ,γ][1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol(B55)

This product was prepared starting from2-O-(2,4-dimethylphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol(B52) and6-chloro-2,10-dimethyl-4,8-bis(1-methylcyclohexyl)-12H-dibenzo[δ,γ][1,3,2]-dioxaphosphocinein a similar manner to Example 54. Yield 71 mg (32.4% of theory). ¹H NMR(400 MHz, C₆D₆) δ, 7.99-6.3 (m, 30H, arom.), 5.44 (m, 1H, CH), 5.14 (m,1H, CH), 4.81 (m, 1H, CH), 4.57 (dd, J=10.7 Hz, J=4.5 Hz, 1H, CH₂), 4.53(m, 1H, CH, CH₂), 4.41 (dd, 1H, J=10.7 Hz, J=4.5 Hz, CH₂), 4.29 (dd, 1H,J=10.8 Hz, J=5.0 Hz, CH₂), 4.18 (dd, 1H, J=10.8 Hz, J=5.0 Hz, CH₂), 3.3(d, J=12.7 Hz, 1H, CH₂), 2.59 (s, 3H, CH₃), 2.52 (s, 3H, CH3), 2.24 (s,3H, CH₃), 2.22 (s, 3H, CH₃), 2.18 (s, 3H, CH₃), 2.17 (s, 3H, CH₃),1.68-1.57 (m, CH₂), 1.48 (s, 3H, CH₃), 1.47 (s, 3H, CH₃), 1.36 (s, 9H,CH₃), 1.33 (s, 9H, CH₃). ³P NMR (161.9 MHz, CDCl₃) δ, 128.7, 105.3.

Iridium-Catalysed Hydrogenation of Imines and Enamides

Examples 56-78

0.01 Molar equivalent of transition metal compound and 0.012 molarequivalent of ligand were dissolved under argon in degassed CH₂Cl₂(0.015 M) and stirred at room temperature for {fraction (1/2)} hour.After adding one molar equivalent of substrate in degassed CH₂Cl₂ (0.15M) under argon, the mixture obtained was hydrogenated in an autoclave atthe appropriate temperature under hydrogen pressure. Conversion and eewere determined by chromatography.Ligands:

Substrates:

The results of the hydrogenations are compiled in Table 2. TABLE 2Substrate/ Metal T P Time metal Conversion ee Examples Substrates Ligandprecursor Additive (° C.) (bar) (h) (mol) (%) (%) 56 S4 B6 [Ir(cod)₂]BF₄— 25 70 16 100 100 65 57 S4 B51 [Ir(cod)₂]BF₄ — 25 70 16 100 100 31 58S4 B50 [Ir(cod)₂]BF₄ — 25 70 16 100 97 71 59 S4 B50 [Ir(cod)₂]BF₄  4% 2570 16 100 99 70 phthalimide 60 S4 B50 [Ir(cod)₂]BF₄  4% 25 70 16 100 4152 BzNH₂ 61 S5 B54 [Ir(cod)₂]BF₄ — 25 70 16 100 86 73 62 S5 B54[Ir(cod)₂]BF₄ — 25 70 0.5 100 24 68 63 S5 B54 [Ir(cod)₂]BF₄ — 0 70 2 1004 40 64 S5 B54 [Ir(cod)₂]BF₄ 10% I₂ 0 70 2 100 1 76 65 S5 B54[Ir(cod)₂]BF₄ — 50 70 0.5 100 80 61 66 S5 B54 [Ir(cod)₂]BF₄ 10% 25 70 16100 89 75 phthalimide 67 S5 B54 [Ir(cod)₂]BF₄ 10% 25 70 16 100 91 75BzNH₂ 68 S5 B55 [Ir(cod)₂]BF₄ 10% 25 70 16 100 63 54 phthalimide 69 S5B55 [Ir(cod)₂]BF₄ 10% 25 70 16 100 81 58 BzNH₂ 70 S6 B6 [Rh(nbd)₂]PF₆ —25 3.5 24 100 100 48 71 S6 B51 [Rh(nbd)₂]PF₆ — 25 3.5 24 100 99 6 72 S6B50 [Rh(nbd)₂]PF₆ — 25 3.5 24 100 100 33 73 S6 B53 [Rh(nbd)₂]PF₆ — 253.5 24 100 98 20 74 S6 B54 [Rh(nbd)₂]PF₆ — 25 3.5 24 100 97 22 75 S6 B6[Rh(nbd)₂]PF₆ — 25 3.5 24 100 56 40 76 S6 B51 [Rh(nbd)₂]PF₆ — 25 3.5 24100 89 50 77 S6 B50 [Rh(nbd)₂]PF₆ — 25 3.5 24 100 89 28 78 S6 B54[Rh(cod)₂]BF₄ — 25 3.5 24 100 98 27

Example 79

In an autoclave, 28.1 mg (0.022 mmol) of [Ir(cod)(B6)]BF₄ (B18) and 0.39g(2 mmol) N-(phenylethylidene)aniline (S4) were dissolved in 10 ml ofdegassed CH₂Cl₂. The mixture was hydrogenated at room temperature and 50bar of hydrogen pressure. Conversion and ee were determined by gaschromatography. 99% conversion, 67% ee.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims.

1. Compounds of the formula (I),

where *1, *2, *3 and *4 are each independently a stereogenic carbon atomwhich is in the R- or S-configuration, X¹ and X² are each independentlyabsent or are oxygen and R¹ and R² may each independently be: hydrogen,C₁-C₂₀-alkyl, C₁-C₂₀-fluoroalkyl, C₂-C₂₀-alkenyl, C₄-C₂₄-aryl,C₅-C₂₅-arylalkyl, C₆-C₂₆-arylalkenyl or NR⁷R⁸, OR⁸, —(C₁-C₈-alkyl)-OR⁸,—(C₁-C₈-alkyl)-NR⁷R⁸ or —O₂CR⁸ where R⁷ and R⁸ are each independentlyC₁-C₈-alkyl, C₅-C₁₄-arylalkyl or C₄-C₁₅-aryl, or R⁷ and R⁸ together area cyclic amino radical having a total of 4 to 20 carbon atoms,  or R¹and R² are each independently radicals of the formula (II)—R⁹—SiR¹⁰R¹¹R¹²  (II)  where R⁹ is absent, or is oxygen or methylene andR¹⁰, R¹¹ and R¹² are each independently C₁-C₁₂-alkyl, C₅-C₁₅-arylalkylor C₄-C₁₄-aryl and R³, R⁴, R⁵ and R⁶ are each independently R¹³, OR¹⁴ orNR¹⁵R¹⁶ where R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently C₁-C₁₂-alkyl,C₅-C₁₅-arylalkyl or C₄-C₁₄-aryl, or NR¹⁵R¹⁶ together is a cyclic aminoradical having 4 to 20 carbon atoms, or R³ and R⁴ and/or R⁵ and R⁶ ineach case together are —O—R¹⁷—O— where R¹⁷ is a radical selected fromthe group of C₂-C₄-alkylene, 1,2-phenylene, 1,3-phenylene,1,2-cyclohexylene, 1,1′-ferrocenylene, 1,2-ferrocenylene,2,2′-(1,1′-binaphthylene), 2,2′-(1,1′)-biphenylene and1,1′-(diphenyl-2,2′-methylene)-diyl, and the radicals mentioned mayoptionally be mono- or polysubstituted by radicals selected from thegroup of fluorine, chlorine, C₁-C₈-alkoxy and C₁-C₈-alkyl.
 2. Compoundsaccording to claim 1, where, in formula (I), ¹, ^(*2), ^(*3), ^(*4)together define the following stereoisomers of the central substitutedfuran ring: (1R,2R,3R,4R), (1R,2R,3R,4S), (1R,2R,3S,4S), (1R,2S,3S,4S),(1R,2S,3R,4S), (1R,2S,3S,4R), (1R,2R,3S,4R), (1S,2S,3R,4S),(1S,2S,3S,4S), (1S,2S,3S,4R), (1S,2S,3R,4R), (1S,2R,3R,4R),(1S,2R,3S,4R), (1S,2R,3R,4S), (1S,2S,3R,4S), (1R,2R,3S,4R).
 3. Compoundsaccording to claim 1, characterized in that, in formula (I), R¹ and R²are each independently hydrogen, C₁-C₄-alkyl, C₄-C₁₄-aryl, O—R⁸, O₂C—R⁸where R⁸ is C₁-C₁₂-alkyl, C₅-C₂₅-arylalkyl or C₄-C₁₄-aryl, orOSiR¹⁰R¹¹R¹², and R¹⁰, R¹¹, and R¹² are each independently C₁-C₁₂-alkylor C₄-C₁₄-aryl.
 4. Compounds according to claim 1, characterized inthat, in formula (I), R¹ and R² are each independently hydrogen,tert-butoxy, trityloxy, tert-butyldimethylsilyloxy,tert-butyldiphenylsilyloxy, trimethylsilyloxy, triethylsilyloxy,triisopropylsilyloxy, neopentoxy or 1-adamantoxy.
 5. Compounds accordingto claim 1, characterized in that, in formula (I), R³, R⁴, R⁵ and R⁶ areeach independently R¹³, OR¹⁴ or NR¹⁵R¹⁶ where R¹³, R¹⁴, R¹⁵ and R¹⁶ areeach independently C₁-C₁₂-alkyl or C₄-C₁₄-aryl, or NR¹⁵R¹⁶ together is acyclic amino radical having 4 to 12 carbon atoms, or R³ and R⁴ and/or R⁵and R⁶ together are each —O—R¹⁷—O— where R¹⁷ is ethylene, 1,2-phenylene,1,3-phenylene, 1,2-cyclohexylene, 1,1′-ferrocenylene, 1,2-ferrocenylene,di- or tetra-C₁-C₈-alkyl-substituted1,1′-(diphenyl-2,2′-methylene)-diyl, 2,2′-(1,1′-binaphthylene) or2,2′-(1,1′)-biphenylene, and 2,2′-(1,1′-binaphthylene) or2,2′-(1,1′)-biphenylene is substituted at least in the 6,6′-position byradicals selected from the group of C₁-C₈-alkoxy and C₁-C₈-alkyl, andmay also be substituted in the 5,5′-,4,4′-, 3,3′- or 2,2′-position byradicals selected from the group of fluorine, chlorine, C₁-C₈-alkoxy andC₁-C₈-alkyl.
 6. Compounds according to claim 1, characterized in that,in formula (I), R³, R⁴, R⁵ and R⁶ are each independently R¹³, OR¹⁴ orNR¹⁵R¹⁶ where R¹³ and R¹⁴ are each independently methyl, ethyl,n-propyl, isopropyl, tert-butyl, cyclohexyl, phenyl,2-(C₁-C₈)-alkylphenyl, 3-(C₁-C₈)-alkylphenyl, 4-(C₁-C₈)-alkylphenyl,2,6-di-(C₁-C₈)-alkylphenyl, 3,5-di-(C₁-C₈)-alkylphenyl,2,4-di-(C₁-C₈)-alkylphenyl, 3,4,5-tri-(C₁-C₈)-alkylphenyl,2-(C₁-C₈)-alkoxyphenyl, 3-(C₁-C₈)-alkoxyphenyl, 4-(C₁-C₈)-alkoxyphenyl,2,4-di-(C₁-C₈)-alkoxyphenyl, 2,6-di-(C₁-C₈)-alkoxyphenyl,3,5-di-(C₁-C₈)-alkoxyphenyl, 3,4,5-tri-(C₁-C₈)-alkoxyphenyl,3,5-dialkyl-4-(C₁-C₈)-alkoxyphenyl,3,5-(C₁-C₈)-dialkyl-4-di-(C₁-C₈)-alkylaminophenyl,4-di-(C₁-C₈)-alkylaminophenyl, 3,5-bis-((C₁-C₄)-fluoroalkyl),2,4-bis-((C₁-C₄)-fluoroalkyl)phenyl, 4-((C₁-C₄)-fluoroalkyl)phenyl andmono-, di-, tri- or tetra-fluorine- and/or -chlorine-substituted phenyl,fluorenyl or naphthyl or NR¹⁵R¹⁶ as a whole is dimethylamino,diethylamino, pyrrolidino or diisopropylamino or R³ and R⁴ and/or R⁵ andR⁶, each in pairs, are O—R¹⁷—O where R¹⁷ is1,1′-bis-(4,6-di-(C₁-C₈-alkyl)-phenyl)-2,2′-methylene)-diyl or where R¹⁷is (R)-1,1′-biphenyl-2,2′-diyl, (S)-1,1′-biphenyl-2,2′-diyl,(R)-1,1′-binaphthyl-2,2′-diyl, (S)-1,1′-binaphthyl-2,2′-diyl,1,1′-[bis-(4-methyl-6-tert-butylphenyl)-2,2′-methylene)]-diyl or1,1′-[bis-(4-methyl-6-(1-methylcyclohexyl)-2,2′-methylene)]-diyl. 7.Compounds according to claim 1, characterized in that, in formula (I),R³ and R⁴ and/or R⁵ and R⁶ in pairs are identical.
 8. Compoundsaccording to claim 1, characterized in that they are of formula (Ia) to(Ii)

where ^(*1), ^(*2), ^(*3), ^(*4), R¹, R², R¹³, R¹⁴, R¹⁵ and R¹⁶ are eachas defined under formula (I) in claim
 1. 9. Compounds of the formula(XIII),

where R¹, R², R³ and R⁴ are each as defined under formula (I) inclaim
 1. 10. Compounds selected from the group consisting of2,3-bis-O-(Diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-L-iditol,2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-L-iditol,2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-L-iditol,2,3-bis-O-(di(4-methoxyphenyl)phosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol,2,3-bis-O-(di((4-Trifluoromethyl)phenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol,2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol,2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(4,8-ditert-butyl-2,10-dimethyl-12H-dibenzo-[δ,γ][1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitoland2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(2,10-dimethyl-4,8-bis(1-methylcyclohexyl)-12H-dibenzo[δ,γ]-[1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol.11. Process for preparing compounds of the formula (XV)

where R¹, R², R⁵, R⁶ and R¹³ are each as defined under formula (I) inclaim 1, comprising t, in step a) converting compounds of the formula(XVI)

where R¹ and R² are each defined under formula (I) in claim 1, in thepresence of compounds of the formula (XVII)(R¹³)₂PMet²  (XVII) where Met² is lithium, sodium or potassium and R¹³is as defined under formula (I) in claim 1, to compounds of the formula(XVIII)

where R¹, R², Met² and R¹³ are as defined above, and, in step b),reacting the compounds of the formula (XVIII) with compounds of theformula (XIIb)R⁵R⁶P—Y  (XIIb) where R⁵ and R⁶ are each as defined under formula (I) inclaim 1 and Y is chlorine, bromine, iodine, dimethylamino ordiethylamino, to give compounds of the formula (XV).
 12. Processaccording to claim 11, characterized in that the compounds of theformula (XVII) are converted by acidifying to compounds of the formula(XIX)

and, in step b), are converted by reacting with compounds of the formula(XIIb) to compounds of the formula (XV).
 13. Process according to claim12, characterized in that step b) is carried out in the presence of abase.
 14. Compounds of the formula (XVIII)

where R¹, R² and R¹³ are each as defined under formula (I) in claim 1and Met² is as defined under formula (XVII) in claim
 10. 15. Compoundsof the formula (XIX)

where R¹, R² and R¹³ are each as defined under formula (I) in claim 1.16. Compounds of the formula (XXa)

where R¹ and R² are each as defined under formula (I) in claim
 1. 17.Compounds of the formula (XXIa),

where R¹, R² and R¹³ are each as defined under formula (I) in claim 1and Met² is as defined under formula (XVII) in claim
 10. 18. Compoundsof the formula (XXIb),

where R¹, R² and R¹³ are each as defined under formula (I), and R¹⁹ isC₁-C₁₂-alkyl, C₁-C₁₂-fluoroalkyl, C₅-C₂₅-arylalkyl or C₄-C₂₄-aryl. 19.Transition metal complexes containing compounds according to claim 1.20. Transition metal complexes according to claim 19, characterized inthat the transition metal is selected from the group of ruthenium,osmium, cobalt, rhodium, iridium, nickel, palladium, platinum andcopper.
 21. Transition metal complexes according to claim 19,characterized in that the molar ratio of transition metal to compoundsof claim 1 is 1:1.
 22. Transition metal complexes according to claim 20,characterized in that they obey the formula (XXIII)[(I)L¹ ₂M]  (XXIII) where (I) represents a compound of the formula (I)as defined in claim 1 and M is rhodium or iridium and L¹ is in each casea C₂-C₁₂-alkene or a nitrile or L¹ ₂ together is a (C₄-C₁₂)-diene. 23.[Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol)]BF₄,[Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol)]BF₄,[Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol)]BF₄and[Ir(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyidiphenylsilyl)-2,5-anhydro-D-mannitol)]BF₄.24. Transition metal complexes according to claim 19, characterized inthat they are obtained by reacting transition metal compounds andcompounds according to claim
 1. 25. Transition metal complexes accordingto claim 24, characterized in that the transition metal compounds usedare: transition metal compounds of the formula (XXIIa)M(An¹)_(q)  (XXIIa) where M is rhodium, iridium, ruthenium, nickel,palladium, platinum or copper and An¹ is chloride, bromide, acetate,nitrate, methanesulphonate, trifluoromethanesulphonate oracetylacetonate and q is 3 for rhodium, iridium and ruthenium, is 2 fornickel, palladium and platinum, and is 1 for copper, or transition metalcompounds of the formula (XXIIb),M(An²)_(q)L¹ ₂  (XXIIb) where M is rhodium, iridium, ruthenium, nickel,paladium, platinum or copper and An² is chloride, bromide, acetate,methanesulphonate or trifluoro-methanesulphonate, tetrafluoroborate orhexafluorophosphate, perchlorate, hexafluoroantimonate,tetra(bis-3,5-trifluromethylphenyl)borate or tetraphenylborate and q is1 for rhodium and iridium, is 2 for ruthenium, nickel, palladium andplatinum, and is 1 for copper, L¹ is in each case a C₂-C₁₂-alkene or L¹₂ together is a (C₄-C₁₂)-diene or transition metal compounds of theformula (XXIIc)[ML²An¹ ₂]₂  (XXIIc) where M is ruthenium and L² is an aryl radical orcyclooctadiene, norbornadiene or methylallyl or transition metalcompounds of the formula (XXIId)Met³ _(q)[M(An³)₄]  (XXIId) where M is palladium, nickel, iridium orrhodium and An³ is chloride or bromide and Met³ is lithium, sodium,potassium, ammonium or organic ammonium and q is 3 for rhodium andiridium, and is 2 for nickel, palladium and platinum, or transitionmetal compounds of the formula (XXIIe)[M(L³)₂]An⁴  (XXIIe) where M is iridium or rhodium and L³ is(C₄-C₁₂)-diene and An⁴ is a noncoordinating or weakly coordinating anionor Ni(1,5-cyclooctadiene)₂, Pd₂(dibenzylideneacetone)₃, Pd[PPh₃]₄,cyclopentadienyl₂Ru, Rh(acac)(CO)₂, Ir(pyridine)₂(1,5-cyclooctadiene),Cu(phenyl)Br, Cu(phenyl)Cl, Cu(phenyl)I, Cu(PPh₃)₂Br, [Cu(CH₃CN)₄]BF₄and [Cu(CH₃CN)₄]PF₆ or multinuclear bridged complexes, for example[Rh(1,5-cyclooctadiene)Cl]₂, [Rh(1,5-cyclooctadiene)Br]₂,[Rh(ethene)₂Cl]₂ or [Rh(cyclooctene)₂Cl]₂.
 26. Transition metalcomplexes according to claim 25, characterized in that the transitionmetal compounds used are: [Rh(cod)Cl]₂, [Rh(cod)Br]₂, [Rh(cod)₂]ClO₄,[Rh(cod)₂]BF₄, [Rh(cod)₂]PF₄, [Rh(cod)₂]ClO₆, [Rh(cod)₂]OTf,[Rh(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl), [Rh(cod)₂]SbF₆,RuCl₂(cod), [(cymene)RuCl₂]₂, [(benzene)RuCl₂]₂, [(mesityl)RuCl₂]₂,[(cymene)RuBr₂]₂, [(cymene)RuI₂]₂, [(cymene)Ru(BF₄)₂]₂,[(cymene)Ru(PF₆)₂]₂, [(cymene)Ru(BAr₄)₂]₂(Ar=3,5-bistrifluoromethylphenyl), [(cymene)Ru(SbF₆)₂]₂, [Ir(cod)Cl]₂,[Ir(cod)₂]PF₆, [Ir(cod)₂]ClO₄, [Ir(cod)₂]SbF₆, [Ir(cod)₂]BF₄,[Ir(cod)₂]OTf, [Ir(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl), RuCl₃,NiCl₃, RhCl₃, PdCl₂, PdBr₂, Pd(OAc)₂, Pd₂(dibenzylideneacetone)₃,Pd(acetylacetonate)₂, CuOTf, CuI, CuCl, Cu(OTf)₂, CuBr, CuI, CuBr₂,CuCl₂, CuI₂, [Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)₂]ClO₄, [Rh(nbd)₂]BF₄,[Rh(nbd)₂]PF₆, [Rh(nbd)₂]OTf, [Rh(nbd)₂]BAr₄(Ar=3,5-bistrifluoromethylphenyl), [Rh(nbd)₂]SbF₆, RuCl₂(nbd),[Ir(nbd)₂]PF₆, [Ir(nbd)₂]ClO₄, [Ir(nbd)₂]SbF₆, [Ir(nbd)₂]BF₄,[Ir(nbd)₂]OTf, [Ir(nbd)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl),Ir(pyridine)₂(nbd), [Ru(DMSO)₄Cl₂], [Ru(CH₃CN)₄Cl₂], [Ru(PhCN)₄C[₂],[Ru(cod)Cl₂]_(n), [Ru(cod)₄(methallyl)₂], [Ru(acetylacetonate)₃]. 27.Transition metal complexes according to claim 26, characterized in thatthe transition metal compounds used are: [Rh(cod)Cl]₂, [Rh(cod)Br]₂,[Rh(cod)₂]ClO₄, [Rh(cod)₂]BF₄, [Rh(cod)₂]PF₄, [Rh(cod)₂]CIO₆,[Rh(cod)₂]OTf, [Rh(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl),[Rh(cod)₂]SbF₆, [Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)₂]ClO₄,[Rh(nbd)₂]BF₄, [Rh(nbd)₂]PF₆, [Rh(nbd)₂]OTf, [Rh(nbd)₂]BAr₄(Ar=3,5-bistrifluoromethylphenyl), [Rh(nbd)₂]SbF₆, [Ir(cod)Cl]₂,[Ir(cod)₂]PF₆, [Ir(cod)₂]ClO₄, [Ir(cod)₂]SbF₆, [Ir(cod)₂]BF₄,[Ir(cod)₂]OTf, [Ir(cod)₂]BAr₄ (Ar=3,5-bistrifluoromethylphenyl). 28.Transition metal complexes according to claim 23, characterized in thatthe amount of the transition metal compounds used is 25 to 200 mol %,based on the compound according to claim
 1. 29. A process for preparingstereoisomerically enriched compounds comprising providing transitionmetal compexes of claim
 19. 30. The process according to claim 29,characterized in that the stereoisomerically enriched compounds areobtained by asymmetric 1,4-additions, asymmetric hydroformylations,asymmetric hydrocyanations, asymmetric Heck reactions and asymmetrichydrogenations.
 31. A process for preparing active ingredients inpharmaceuticals and agrochemicals, or intermediates of these two classescomprising providing stereoisomerically enriched compounds of claim 29.32. A process for catalyzing reactions comprising providing metalcomplexes according to claim
 19. 33. Process for preparingstereoisomerically enriched compounds by catalytic hydrogenations ofolefins, enamines, enamides, imines or ketones, 1,4-additions,hydroformylations, hydrocyanations or Heck reactions, characterized inthat the catalysts used are those which comprise transition metalcomplexes according to claim
 19. 34. Process according to claim 33,characterized in that the amount of the transition metal complexes usedis 0.001 to 5 mol %, based on the substrate used.
 35. Process accordingto claim 33, characterized in that the stereoisomerically enrichedcompounds are obtained by catalytic hydrogenation of olefins, enamidesor imines.
 36. Process according to claim 33, characterized in that theworking temperature is −20° C. to 200° C.
 37. Process according to claim34, characterized in that the hydrogen pressure is 0.1 to 200 bar. 38.Catalysts comprising transition metal complexes according to claim 19.